Functionalized F-POSS monomer compositions and uses thereof

ABSTRACT

Functionalized F-POSS compounds comprising synthetic blends of at least two feedstocks that produce a distribution of fluorinated polyhedral oligomeric silsesquioxane molecule structures and/or functional groups.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a continuation-in-part of U.S. patent applicationSer. No. 15/065,289, filed on Mar. 9, 2016, which claims benefit of U.S.Provisional Patent Application No. 62/130,170, filed on Mar. 9, 2015,and is a continuation-in-part of U.S. patent application Ser. No.15/230,697, filed on Aug. 8, 2016, which is a continuation of U.S.patent application Ser. No. 14/876,911, filed on Oct. 7, 2015, whichclaims benefit of U.S. Provisional Patent Application No. 62/060,622,filed on Oct. 7, 2014, and commonly assigned to the assignee of thepresent application, the disclosures of which are incorporated byreference in their entirety herein.

FIELD

The present disclosure relates, in exemplary embodiments, tofunctionalized F-POSS compounds comprising synthetic blends of at leasttwo feedstocks that produce a distribution of fluorinated polyhedraloligomeric silsesquioxane molecule structures and/or functional groups.The present disclosure also relates, in exemplary embodiments, tomethods of making such compounds, and uses thereof.

BACKGROUND

Fluorinated polyhedral oligomeric silsesquioxane (“F-POSS”) moleculesare a subclass of polyhedral oligomeric silsesquioxanes (“POSS”) whichconsists of a silicon-oxide core [SiO_(1.5)] with a periphery oflong-chain fluorinated alkyl groups. F-POSS molecules possesses one ofthe lowest known surface energies leading to the creation ofsuperhydrophobic and oleophobic surfaces. A feature of F-POSS materialis that it ordinarily forms a siloxy cage that acts like an inorganicglass-like material, but have organic R group substituents at the matrixapices, which provides unusual properties and applications. See FormulaI below.

F-POSS molecules find application in material science. For example,superhydrophobic and superoleophobic surfaces have been produced usingF-POSS, either cast on a substrate or blended into a polymer matrix.See, for example, Chhatre, S. S.; Guardado, J. O.; Moore, B. M.; Haddad,T. S.; Mabry, J. M.; McKinley, G. H.; Cohen, R. E. ACS Appl. Mater.Interfaces 2010, 2, 3544-3554; Mabry, J. M.; Vij, A.; Iacono, S. T.;Viers, B. D. Angew. Chem., Int. Ed. 2008, 47, 4137-4140; Tuteja, A.;Choi, W.; Mabry, J. M.; McKinely, G. H.; Cohen, R. E. Proc. Natl. Acad.Sci. U.S.A. 2008, 105, S18200/1-S18200/29; and Tuteja, A.; Choi, W.; Ma,M.; Mabry, J. M.; Mazzella, S. A.; Rutledge, G. C.; McKinley, G. H.;Cohen, R. E. Science 2007, 318, 1618-1622.

It would be desirable to provide novel functionalized F-POSS compoundsfor use in materials.

SUMMARY

In exemplary embodiments, a compound of the formula is provided:

wherein R¹ is a long chain fluorinated alkyl; R² is selected from thegroup consisting of C₁-C₈ alkyl, C₂-C₈ alkenyl, C₂-C₈ alkynyl, C₆-C₁₀aryl, C₃-C₈ cycloalkyl, 5-7 membered heterocyclic and 5-7 memberedheteroaryl, wherein each hydrogen atom in R¹ is independently optionallysubstituted by an R³; each R³ is independently selected from the groupconsisting of halo (i.e., any haloalkane, or alkane containing at leastone atom of a halogen), C₁-C₈ alkyl, C₂-C₈ alkenyl, C₂-C₈ alkynyl,C₆-C₁₀ aryl, C₃-C₈ cycloalkyl, 5-7 membered heterocyclic, 5-7 memberedheteroaryl, —NCO, —OR⁴, —NR⁴R⁵, —OC(O)R⁴, —C(O)OR⁴, —C(O)R⁴, —OC(O)OR⁴,—C(O)NR⁴R⁵, —OC(O)NR⁴R⁵, —NR⁴C(O)R⁵, —NR⁴C(O)OR⁵ and —NR⁴C(O)NR⁴R⁵, andwhen R³ is C₁-C₈ alkyl, C₂-C₈ alkenyl, C₂-C₈ alkynyl, C₆-C₁₀ aryl, C₃-C₈cycloalkyl, 5-7 membered heterocyclic or 5-7 membered heteroaryl, eachhydrogen atom in R³ is independently optionally substituted by an R⁶;each R⁴ and R⁵ is independently selected from the group consisting ofhydrogen, C₁-C₈ alkyl, C₂-C₈ alkenyl, C₂-C₈ alkynyl, C₆-C₁₀ aryl, C₃-C₈cycloalkyl, 5-7 membered heterocyclic, and 5-7 membered heteroaryl,wherein each hydrogen atom in R⁴ and R⁵ is independently optionallysubstituted by an R⁶; each R⁶ is independently selected from the groupconsisting of halo, C₁-C₈ alkyl, C₂-C₈ alkenyl, C₂-C₈ alkynyl, C₆-C₁₀aryl, C₃-C₈ cycloalkyl, 5-7 membered heterocyclic, 5-7 memberedheteroaryl, —NCO, —OR⁷, —NR⁷R⁸, —OC(O)R⁷, —C(O)OR⁷, —C(O)R⁷, —OC(O)OR⁷,—C(O)NR⁷R⁸, —OC(O)NR⁷R⁸, —NR⁷C(O)R⁸, —NR⁷C(O)OR⁸ and —NR⁷C(O)NR⁷R⁸, andwhen R⁶ is C₁-C₈ alkyl, C₂-C₈ alkenyl, C₂-C₈ alkynyl, C₆-C₁₀ aryl, C₃-C₈cycloalkyl, 5-7 membered heterocyclic or 5-7 membered heteroaryl, eachhydrogen atom in R⁶ is independently optionally substituted by an R⁹;each R⁷ and R⁸ is independently selected from the group consisting ofhydrogen, C₁-C₈ alkyl, C₂-C₈ alkenyl, C₂-C₈ alkynyl, C₆-C₁₀ aryl, C₃-C₈cycloalkyl, 5-7 membered heterocyclic and 5-7 membered heteroaryl,wherein each hydrogen atom in R⁷ and R⁸ is independently optionallysubstituted by one or more R⁹; each R⁹ is independently selected fromthe group consisting of hydrogen, halo, C₁-C₈ alkyl, C₂-C₈ alkenyl,C₂-C₈ alkynyl, C₆-C₁₀ aryl, C₃-C₈ cycloalkyl, 5-7 membered heterocyclic,5-7 membered heteroaryl, —NCO, —OR¹⁰, —NR¹⁰R¹¹, —OC(O)R¹⁰, —C(O)OR¹⁰,—C(O)R¹⁰, —OC(O)OR¹⁰, —C(O)NR¹⁰R¹¹, —OC(O)NR¹⁰R¹¹, —NR¹⁰C(O)R¹¹,—NR¹⁰C(O)OR¹¹ and —NR¹⁰C(O)NR¹⁰R¹¹, and when R⁹ is C₁-C₈ alkyl, C₂-C₈alkenyl, C₂-C₈ alkynyl, C₆-C₁₀ aryl, C₃-C₈ cycloalkyl, 5-7 memberedheterocyclic, C₃-C₈ cycloalkyl or 5-7 membered heteroaryl, each hydrogenin R⁹ is independently optionally substituted by a moiety selected fromthe group consisting of halo, —NCO, —OR¹⁰, —NR¹⁰R¹¹, —OC(O)R¹⁰,—C(O)OR¹⁰, —C(O)R¹⁰, —OC(O)OR¹⁰, —C(O)NR¹⁰R¹¹, —OC(O)NR¹⁰R¹¹,—NR¹⁰C(O)R¹¹, —NR and NR each R¹⁰ and R¹¹ is independently selected fromthe group consisting of H, C₁-C₈ alkyl, C₂-C₈ alkenyl and C₂-C₈ alkynyl,and when R¹⁰ or R¹¹ are C₁-C₈ alkyl, C₂-C₈ alkenyl or C₂-C₈ alkynyl,each hydrogen atom in R¹⁰ and R¹¹ is independently optionallysubstituted by a fluorine atom; n is an integer from 0 to 8; and each ofR¹ and R² is independently covalently attached at a silicon atom.

In some aspects of these embodiments, R² is C₁-C₈ alkyl, wherein eachhydrogen atom in R² is independently optionally substituted by an R³. Inother aspects of these embodiments, R³ is —NCO, —OR⁴, —OC(O)R⁴,—C(O)OR⁴, —C(O)R⁴ or —OC(O)OR⁴. In other aspects of these embodiments,R⁴ is C₁-C₈ alkyl, wherein each hydrogen atom in R⁴ is independentlyoptionally substituted by an R⁶. In other aspects of these embodiments,R⁴ is C₂-C₈ alkenyl, wherein each hydrogen atom in R⁴ is independentlyoptionally substituted by an R⁶. In other aspects of these embodiments,R⁶ is C₁-C₈ alkyl, —NCO, —OR⁷, —NR⁷R⁸, —OC(O)R⁷, —C(O)OR⁷, —C(O)R⁷ or—OC(O)OR⁷. In other aspects of these embodiments, R⁷ is C₁-C₈ alkyl,C₂-C₈ alkenyl, C₂-C₈ alkynyl, C₆-C₁₀ aryl or 5-7 membered heteroaryl,wherein each hydrogen atom in R⁷ is independently optionally substitutedby one or more R⁹. In other aspects of these embodiments, R⁹ is hydrogenor C₁-C₈ alkyl, and when R⁹ is C₁-C₈ alkyl, R⁹ is optionally substitutedby a —OC(O)R¹⁰. In other aspects of these embodiments, R¹⁰ is H or C₁-C₈alkyl, and when R¹⁰ is C₁-C₈ alkyl, each hydrogen atom in R¹⁰ isindependently optionally substituted by a fluorine atom.

In other aspects of these embodiments, R² is n-propyl, wherein eachhydrogen atom in R² is independently optionally substituted by an R³. Inother aspects of these embodiments, R³ is —OC(O)R⁴ or —OC(O)OR⁴. Inother aspects of these embodiments, R⁴ is n-propyl, optionallysubstituted by an R⁶. In other aspects of these embodiments, R⁴ is—CH═CH₂, wherein each hydrogen atom in R⁴ is independently optionallysubstituted by an R⁶. In other aspects of these embodiments, R⁶ is C₁-C₈alkyl. In other aspects of these embodiments, R⁶ is methyl.

In other aspects of these embodiments, R⁶ is —OC(O)R⁷ or —C(O)OR⁷. Inother aspects of these embodiments, R⁷ is —CH═CH₂, optionallysubstituted by an R⁹. In other aspects of these embodiments, R⁹ is C₁-C₈alkyl. In other aspects of these embodiments, R⁹ is methyl.

In other embodiments, R² is C₆-C₁₀ aryl, wherein each hydrogen atom inR² is independently optionally substituted by an R³. In some aspects ofthese embodiments, R³ is C₁-C₈ alkyl, C₂-C₈ alkenyl or NCO, and when R³is C₁-C₈ alkyl or C₂-C₈ alkenyl, each hydrogen atom in R³ isindependently optionally substituted by an R⁶. In other aspects of theseembodiments, R³ is C₂-C₈ alkenyl, wherein each hydrogen atom in R³ isindependently optionally substituted by an R⁶. In other aspects of theseembodiments, R³ is —CH═CH₂, wherein each hydrogen atom in R³ isindependently optionally substituted by an R⁶. In other aspects of theseembodiments, R⁶ is methyl. In other aspects of these embodiments, R³ isC₁-C₈ alkyl, wherein each hydrogen atom in R³ is independentlyoptionally substituted by an R⁶. In other aspects of these embodiments,R⁶ is C₆-C₁₀ aryl, wherein each hydrogen atom in R⁶ is independentlyoptionally substituted by an R⁹. In other aspects of these embodiments,R⁹ is C₂-C₈ alkenyl or NCO, and when R⁹ is C₂-C₈ alkenyl, each hydrogenatom in R⁹ is independently optionally substituted by a moiety selectedfrom the group consisting of halo, —NCO, —OR¹⁰, —NR¹⁰R¹¹, —OC(O)R¹⁰,—C(O)OR¹⁰, —C(O)R¹⁰, —OC(O)OR¹⁰, —C(O)NR¹⁰R¹¹, —OC(O)NR¹⁰R¹¹,—NR¹⁰C(O)R¹¹, —NR¹⁰C(O)OR¹¹ and —NR¹⁰C(O)NR¹¹. In other aspects of theseembodiments, R⁹ is —CH═CH₂. In other aspects of these embodiments, R⁹ is—NCO.

In other embodiments, R² is C₂-C₈ alkenyl, wherein each hydrogen atom inR² is independently optionally substituted by an R³. In some aspects ofthese embodiments, R³ is halo.

In some embodiments, the long chain fluorinated alkyl is 8/2, 6/2 or4/2.

In some embodiments, the long chain fluorinated alkyl is 6/2, and R² isC₁-C₈ alkyl. In some embodiments, the long chain fluorinated alkyl is6/2, and R² is C₁-C₈ alkyl. In some embodiments, the long chainfluorinated alkyl is 6/2, and R² is propyl. In some embodiments, thelong chain fluorinated alkyl is 6/2, and R² is C₁-C₈ alkyl, substitutedby one —OC(O)R⁴. In some embodiments, the long chain fluorinated alkylis 6/2, and R² is C₁-C₈ alkyl, substituted by one R³ that is —OC(O)R⁴,and R⁴ is C₁-C₈ alkyl. In some embodiments, the long chain fluorinatedalkyl is 6/2, and R² is propyl acetate.

In another embodiment, the disclosure provides an article comprising asynthetic blend copolymer as described herein. In some aspects of theseembodiments, the synthetic blend copolymer is made from polymerizationof a compound as described herein bearing at least one polymerizablegroup, such as an acrylate, with at least one suitable monomer. In someaspects of these embodiments, the suitable monomer is an acrylatemonomer, such as a methacrylate or a methylmethacrylate.

In another embodiment, the disclosure provides an article comprising oneor more compounds of the formula

wherein n, R¹ and R² are as defined herein. In some aspects of theseembodiments, the compound used in the article can that of any of theembodiments described above.

In another embodiment, the disclosure provides an article comprising oneor more compounds of the formula

wherein n, R¹ and R² are as defined herein, produced by the process asdescribed herein. In some aspects of these embodiments, the compoundused in the article can that of any of the embodiments described above.

Other features will become apparent upon reading the following detaileddescription of certain exemplary embodiments, when taken in conjunctionwith the appended claims.

BRIEF DESCRIPTION OF THE DRAWINGS

The drawings disclose exemplary embodiments in which like referencecharacters designate the same or similar parts throughout the figures ofwhich:

FIG. 1 is an analysis plot of ¹H NMR analysis for synthetic blend of 4/2Precursor (1H,1H,2H,2H-nonafluorohexyltriethoxysilane) and3-methacryloxypropyl-triethoxysilane according to Example 1.

FIG. 2 is an analysis plot of ¹⁹F NMR analysis for 10% 4/2 FPOSS-MAsynthetic blend MMA copolymer according to Example 2.

FIG. 3 is a graph of experiments showing the contact angle of water on4/2 FPOSS-MA synthetic blend MMA copolymer (8% solids) on glassaccording to Example 3.

FIG. 4 is a graph of experiments showing the contact angle of hexadecaneon 4/2 FPOSS-MA synthetic blend MMA copolymer (8% solids) on glassaccording to Example 3.

DEFINITIONS

As used herein, the term “long-chain fluorinated alkyl” means anystraight chain or branched chain alkyl group having from 5 to 12 carbonatoms in the longest continuous chain of carbon atoms as counted fromthe point of attachment of the chain of carbon atoms to the silicon atomat any apex of the silicon-oxide core, where at least one hydrogen atomin the straight chain or branched chain alkyl group is replaced by afluorine atom. Any number of hydrogen atoms in the straight chain orbranched chain alkyl group can be replaced with fluorine atoms withinthe meaning of “long-chain fluorinated alkyl” as used herein. Forexample, the terminal methyl group of a straight chain alkyl grouphaving six carbon atoms in the chain (e.g. a hexyl group) can have eachof the pendent hydrogen atoms replaced by a fluorine atom (e.g. atrifluoromethyl) to provide a long chain fluorinated alkyl group havingthe formula —CH₂CH₂CH₂CH₂CH₂CF₃. In another example, the last two carbonatoms of a straight chain alkyl group having six carbon atoms in thechain can have each of the pendent hydrogen atoms replaced by a fluorineatom (e.g. a trifluoroethyl) to provide a long chain fluorinated alkylgroup having the formula —CH₂CH₂CH₂CH₂CF₂CF₃. This exemplary pattern canbe continued to include within the definition of “long chain fluorinatedalkyl” groups of the formula —CH₂CH₂CH₂CF₂CF₂CF₃, —CH₂CH₂CF₂CF₂CF₂CF₃,—CH₂CF₂CF₂CF₂CF₂CF₃, and —CF₂CF₂CF₂CF₂CF₂CF₃. As is commonly known inthe art, an alkyl group where every hydrogen atoms in the chain isreplaced by a fluorine atom is known as a “perfluorinated” alkyl group.

When less than all of the carbon atoms in the longest continuous chainof carbon atoms have hydrogens replaced by fluorine atoms, the “longchain fluorinated alkyl” group can be identified by the shorthand X/Y,where X is the number of terminal carbon atoms in the longest continuouschain of carbon atoms as counted from the point of attachment of thechain of carbon atoms to the silicon atom at any apex of thesilicon-oxide core, and Y is the remaining number of carbon atoms in thelongest continuous chain of carbon atoms on which hydrogen atoms are notreplaced by fluorine atoms. For example, a long chain fluorinated alkylgroup of the formula —CH₂CH₂CF₂CF₂CF₂CF₃ can be given the shorthand 4/2.Other exemplary long chain fluorinated alkyl groups include but are notlimited to 3/3, 6/2, 4/4, 8/2, 6/4 and the like.

When the shorthand X/Y is used herein in connection with F-POSS, thename provided refers to the F-POSS molecule each of the groups attachedto the apices of the silicon-oxide core is of the long chain fluorinatedalkyl group type defined by the X/Y. For example, 6/2 F-POSS refers toan F-POSS molecule of Formula I, wherein each of the R groups at theapices of the silicon-oxide core is a 6/2 long chain fluorinated alkylgroup as defined herein.

As used herein, “alkyl” refers to a saturated aliphatic hydrocarbonradical including straight chain and branched chain groups of 1 to 20carbon atoms (e.g. C₁-C₂₀), preferably 1 to 12 carbon atoms (e.g.C₁-C₁₂), more preferably 1 to 8 carbon atoms (e.g. C₁-C₈), or 1 to 6carbon atoms (e.g. C₁-C₆), or 1 to 4 carbon atoms (e.g. C₁-C₄). “Loweralkyl” refers specifically to an alkyl group with 1 to 4 carbon atoms.Examples of alkyl groups include methyl, ethyl, propyl, 2-propyl,n-butyl, iso-butyl, tert-butyl, pentyl, and the like. Alkyl may besubstituted or unsubstituted. Typical substituent groups include thoseconventionally known in the art, such as cycloalkyl, aryl, heteroaryl,heteroalicyclic, hydroxy, alkoxy, aryloxy, mercapto, alkylthio,arylthio, cyano, halo, carbonyl, thiocarbonyl, O-carbamyl, N-carbamyl,O-thiocarbamyl, N-thiocarbamyl, C-amido, N-amido, C-carboxy, O-carboxy,nitro, silyl, amino and —NR^(x)R^(y), where R^(x) and R^(y) areindependently selected from the group consisting of hydrogen, alkyl,cycloalkyl, aryl, carbonyl, acetyl, sulfonyl, trifluoromethanesulfonyland, combined, a five- or six-member heteroalicyclic ring. Substituentgroups also include those described elsewhere in this disclosure inconnection with alkyl.

As used herein, “cycloaylkyl” refers to a 3 to 10 member all-carbonmonocyclic ring (C₃-C₁₀), an all-carbon 5-member/6-member or6-member/6-member fused bicyclic ring (a “fused” ring system means thateach ring in the system shares an adjacent pair of carbon atoms witheach other ring in the system) wherein one or more of the rings maycontain one or more double bonds but none of the rings has a completelyconjugated pi-electron system. “Cycloalkyl” includes 3 to 8 memberall-carbon monocyclic ring (e.g. “C₃-C₈ cycloalkyl”), Examples, withoutlimitation, of cycloalkyl groups are cyclopropane, cyclobutane,cyclopentane, cyclopentene, cyclohexane, cyclohexadiene, adamantane,cycloheptane, cycloheptatriene, and the like. A cycloalkyl group may besubstituted or unsubstituted. Typical substituent groups include alkyl,aryl, heteroaryl, heteroalicyclic, hydroxy, alkoxy, aryloxy, mercapto,alkylthio, arylthio, cyano, halo, carbonyl, thiocarbonyl, C-carboxy,O-carboxy, O-carbamyl, N-carbamyl, C-amido, N-amido, nitro, amino and—NR^(x)R^(y), with R^(x) and R^(y) as defined above. Substituent groupsalso include those described elsewhere in this disclosure in connectionwith cycloalkyl.

As used herein, “alkenyl” refers to an alkyl group, as defined herein,of at least two carbon atoms in length further defined by the inclusionof at least one carbon-carbon double bond (“C═C”). “Alkenyl” includesgroups having from 2 to 8 carbon atoms and at least one carbon-carbondouble bond (e.g. “C₂-C₈ alkenyl”). Representative examples include, butare not limited to, ethenyl, 1-propenyl, 2-propenyl, 1-, 2-, or3-butenyl, and the like. Alkenyl may be substituted as described abovefor alkyl, or alkenyl may be unsubstituted. Substituent groups alsoinclude those described elsewhere in this disclosure in connection withalkenyl.

As used herein, “alkynyl” refers to an alkyl group, as defined herein,of at least two carbon atoms in length further defined by the inclusionof at least one carbon-carbon triple bond (“C≡C”). “Alkynyl” includesgroups having from 2 to 8 carbon atoms and at least one carbon-carbontriple bond (e.g. “C₂-C₈ alkynyl”). Representative examples include, butare not limited to, ethynyl, 1-propynyl, 2-propynyl, 1-, 2-, or3-butynyl, and the like. Alkynyl may be substituted as described abovefor alkyl, or alkynyl may be unsubstituted. Substituent groups alsoinclude those described elsewhere in this disclosure in connection withalkynyl.

As used herein, “aryl” refers to an all-carbon monocyclic or fused-ringpolycyclic groups of 6 to 14 carbon atoms (C₆-C₁₄) having a completelyconjugated pi-electron system. Aryl includes all-carbon monocyclic orfused-ring polycyclic groups of 6 to 10 carbon atoms (e.g., “C₆-C₁₀aryl”). Examples, without limitation, of aryl groups are phenyl,naphthalenyl and anthracenyl. The aryl group may be substituted asdescribed above for alkyl, or aryl may be unsubstituted. Substituentgroups also include those described elsewhere in this disclosure inconnection with aryl.

As used herein, “heteroaryl” refers to a monocyclic or fused ring groupof 5 to 12 ring atoms containing one, two, three or four ringheteroatoms selected from N, O, and S, the remaining ring atoms being C,and, in addition, having a completely conjugated pi-electron system.“Heteroaryl” includes groups as defined herein having from five to sevenring atoms (e.g., “5-7 membered heteroaryl”). Examples, withoutlimitation, of unsubstituted heteroaryl groups are pyrrole, furan,thiophene, imidazole, oxazole, thiazole, pyrazole, pyridine, pyrimidine,quinoline, isoquinoline, purine, tetrazole, triazine, and carbazole. Theheteroaryl group may be substituted as described above for alkyl, orheteroaryl may be unsubstituted. Substituent groups also include thosedescribed elsewhere in this disclosure in connection with heteroaryl.

As used herein. “heterocyclic” refers to a monocyclic or fused ringgroup having in the ring(s) of 3 to 12 ring atoms, in which one or tworing atoms are heteroatoms selected from N, O, and S(O)_(n) (where n is0, 1 or 2), the remaining ring atoms being C. The rings may also haveone or more double bonds. However, the rings do not have a completelyconjugated pi-electron system. “Heterocyclic” includes groups as definedherein having from five to seven ring atoms (e.g., “5-7 memberedheterocyclic”). The heterocyclic group may be substituted as describedabove for alkyl, or heterocyclic may be unsubstituted. Substituentgroups also include those described elsewhere in this disclosure inconnection with heterocyclic.

As used herein, “alkoxy” refers to both an —O-(alkyl) or an—O-(cycloalkyl) group. “Alkoxy” includes groups having from 1 to 8carbon atoms (e.g., “C₁-C₈ alkoxy”). The alkoxy group may be substitutedas described above for alkyl or it can be unsubstituted. Substituentgroups also include those described elsewhere in this disclosure inconnection with alkoxy. Representative examples include, but are notlimited to, methoxy, ethoxy, propoxy, cyclopropyloxy, cyclobutyloxy,cyclopentyloxy, cyclohexyloxy, and the like.

DETAILED DESCRIPTION

Silsesquioxanes have a cage-like structure, which is most commonly acube, hexagonal prism, octagonal prism, decagonal prism, or dodecagonalprism. In exemplary embodiments, of the various possible F-POSS cagemolecular structures, the cube-like (“T8”) cage structure is provided inconnection with the invention. F-POSS molecules consist of asilicon-oxide core [SiO_(1.5)] with a periphery of long-chainfluorinated alkyl groups.

In exemplary embodiments, the present disclosure provides F-POSScompositions made of a blend of feedstock materials. In one exemplaryembodiment, a first feedstock comprises a long-chain fluorinated alkyltriethoxysilane and a second feedstock comprises a functionalizedtriethoxysilane, where the functionalized triethoxysilane can be of theformula R²Si(OR^(A))₃ where R² is as defined herein and R^(A) is a C₁-C₈alkoxy. The process for preparing compounds described in the disclosurecan be represented by the following scheme.

where R¹, R² and n are as defined herein, and R^(A) can be any alkoxy,for example C₁-C₈ alkoxy. It will be appreciated that the alkoxy can bethe same or different on each of the reagents in the scheme above. Inthe present compositions, the blend of molecules may, in exemplaryembodiments, form a Gaussian distribution of molecules having differentratios of R¹ and R². For example, in one exemplary embodiment, oneportion of the blend may be made up of an F-POSS molecule with a molarratio of R¹:R²=8:0, in other words, all eight apices have R¹ (e.g.,n=8). Another portion may have a molar ratio of R¹:R²=7:1, in otherwords, seven of the apices have R¹ and one apex has R² (e.g., n=7).Another portion has a ratio of 6:2 (e.g., n=6). And, other portions haveratios of 5:3 (e.g., n=5), 4:4 (e.g., n=4), 3:5 (e.g., n=3), 2:6 (e.g.,n=2), 1:7 (e.g., n=1) and 0:8 (e.g., n=0). In exemplary embodiments, thedistribution of R1:R2 ratios generally comprises a Gaussiandistribution. In exemplary embodiments, the distribution of ratios canbe predetermined to an extent, or tuned, based on reaction conditionsand amounts used of each substituent.

It will be further appreciated that the reaction present above is notlimited to two feedstocks. For example, a reaction is contemplated wherea first feedstock comprises a long-chain fluorinated alkyltriethoxysilane, a second feedstock comprises a second long-chainfluorinated alkyl triethoxysilane, and a third feedstock comprises afunctionalized triethoxysilane. Alternatively, a reaction iscontemplated where a first feedstock comprises a long-chain fluorinatedalkyl triethoxysilane, a second feedstock comprises a firstfunctionalized triethoxysilane, and a third feedstock comprises a secondfunctionalized triethoxysilane.

EXAMPLES

The following examples are set forth for purposes of illustration only.Parts and percentages appearing in such examples are by weight unlessotherwise stipulated.

Materials

1H,1H,2H,2H-nonafluorohexyltriethoxysilane was obtained from TCIAmerica. 3-methacryloxypropyltriethoxysilane was obtained from GelestInc. Tetraethylammonium hydroxide in water was obtained from AcrosOrganics (Code 420291000, lot A0322694). Hexafluorobenzene was obtainedfrom Aldrich (H8706-100G, lot MKBS2573V). Diethyl ether was obtainedfrom Acros Organics (61508-5000, lot B0527523).2,2′-Azobis(2-methylpropionitrile), 98%, was obtained fromSigma-Aldrich.

Example 1A: Synthetic Blend 4/2 F-POSS-Methacrylate (SB 4/2 F-POSS-MA)Monomer Synthesis—Synthetic Blend of 4/2 Precursor(1H,1H,2H,2H-nonafluorohexyltriethoxysilane) and3-methacryloxypropyl-triethoxysilane

1.8 g of the 4/2 F-POSS precursor1H,1H,2H,2H-nonafluorohexyltriethoxysilane (MW 410.35; 4.38 mmol) and0.18 g of 3-methacryloxypropyltriethoxysilane (MW 290.43; 0.62 mmol)were taken in a 7:1 molar ratio. To this was added 5 mL of dry THF,followed by the addition of 0.0105 mL of 25% tetraethylammoniumhydroxide solution in water. The reaction mixture was agitated for 5days at room temperature on an orbital shaker then allowed to standundisturbed for another 7 days at room temperature. The reaction mixturewas then concentrated down on a rotary evaporator, the residue taken upin diethyl ether, followed by washing the organic layer with water anddrying over anhydrous MgSO₄. The organic layer was concentrated downagain and the residue dried under vacuum at 50° C. to provide 1.12 g ofthe desired SB 4/2 F-POSS-MA monomer as a gooey solid.

¹H NMR of the product was obtained by dissolving it in hexafluorobenzenewith a few drops of chloroform-d as shown in FIG. 1.

Example 1B: Synthetic Blend 6/2 F-POSS-Propylacetate (SB 6/2F-POSS-Propylacetate) Monomer Synthesis—Synthetic Blend of 6/2 Precursor(1H,1H,2H,2H-Tridecafluorooctyltriethoxysilane) and(3-Acetoxypropyl)trimethoxysilane

A reaction vessel was charged with 15 g of1H,1H,2H,2H-Tridecafluorooctyltriethoxysilane, (Gelest (SIT8175.0, CAS:51851-37-7), 29.5 mmol, 7 eq), 0.935 g of3-Acetoxypropyl)trimethoxysilane (Gelest (SIA0100.0, CAS: 599004-18-1),4.2 mmol, 1 eq) was dissolved in 25 mL of a solution of PotassiumHydroxide (Sigma Aldrich, P1767, CAS 1310-58-3) in Water (DI or Storebought by the gal) and 15 mL of deionized water, followed by 2.5 mL ofaqueous 2-Propanol (Alfa Aesar (36644, 99.5%, CAS 67-63-0), 10 mg/mL).The reaction was stirred for 3 days at room temperature. Theprecipitated solids were filtered to provide 9.84 g (79% yield) of thedesired product.

Mp 121.5° C.; ¹H NMR (AK-225, 500 MHz): δ 0.82 (t, 2H), 1.07-1.05 (m,14H), 1.8 (m, 2H), 2.3-2.21 (m, 14H), 2.52 (s, 3H), 4.05 (t, 2H); ¹⁹FNMR ((CD₃)₂CO, 470 MHz): δ 82.9 (21F), −117.4 (14F), −123.6 (14F),−124.2 (14F), −124.5 (14F), −127.7 (14F); Anal. Calcd forC₆₁H₃₇F₉₁O₁₂Si₈: C, 24.86; H, 1.27; F, 58.65. Found: C, 24.41; H, 1.02;F, 60.55.

Example 1C: Synthetic Blend 6/2 F-POSS-Propylacetate (SB 6/2F-POSS-Propylacetate) Monomer Synthesis—Synthetic Blend of 6/2 Precursor(1H,1H,2H,2H-Tridecafluorooctyltriethoxysilane) and(3-Acetoxypropyl)trimethoxysilane (Scale-Up)

To a 12 L 3NRBF equipped with an overhead stirrer, 2 glass stoppers,cork ring, and a secondary container is charged with stirring, 2.075 Lof Potassium Hydroxide (Sigma Aldrich, P1767, CAS 1310-58-3), 1245 g(2.44 moles) of 1H,1H,2H,2H-Tridecafluorooctyltriethoxysilane, (Gelest(SIT8175.0, CAS: 51851-37-7), 29.5 mmol, 7 eq), 77.61 g (0.351 moles) of3-Acetoxypropyl)trimethoxysilane (Gelest (SIA0100.0, CAS: 599004-18-1).The mixture was stirred for 10 minutes, at which time 210 mL (10 mg/ml)of aqueous 2-Propanol (Alfa Aesar (36644, 99.5%, CAS 67-63-0), followedby 1.245 L of toluene. The reaction mixture was stirred at ambienttemperature for 48-72 hrs. The reaction was filtered, washed withdeionized water, and dried in a vacuum oven to provide 901 g (87.1%yield) of the desired product.

Example 2: Synthesis of 4/2 F-POSS-MA Synthetic Blend MMA Copolymer

Four separate comparison polymerization reactions were run under thesame conditions with varying amounts of SB 4/2 F-POSS-MA monomer. (0, 1,5 and 10 weight percent).

A reaction vessel was charged with 25 mL of 4:1 hexafluorobenzene/THFand degassed for 20 minutes. To the vessel was SB 4/2 F-POSS-MA monomer.(0, 1, 5 and 10 weight percent based on methylmethacrylate monomer),methyl methacrylate monomer (5 g total batch size), and 20 mg of2,2′-azobis(2-methylpropionitrile) initiator. The reaction was run undernitrogen for 18 hours at 70° C. The reaction solution was poured into150 mL of hexane and stirred with a spatula to break up the clumps. Thesolid material was filtered, washed thoroughly with hexane, and driedunder high vacuum at 45° C. overnight. Polymer yields are shown inTable 1. Each polymer was determined to be soluble in Acetone, Methylethyl ketone, Tetrahydrofuran, Acetonitrile. The polymers were notsoluble in Isopropanol. ¹⁹F NMR was performed on the 10% 4/2 FPOSS-MASynthetic Blend MMA copolymer. The NMR shows the incorporation offluorine into the copolymer (See FIG. 2).

Polymer Yields:

TABLE 1 Reaction Yield 0% SB 4/2 F-POSS-MA monomer 2.38 g 1% SB 4/2F-POSS-MA monomer 3.11 g 5% SB 4/2 F-POSS-MA monomer 2.18 g 10% SB 4/2F-POSS-MA monomer 2.37 g

Example 3: 4/2 F-POSS-MA Synthetic Blend MMA Copolymer Contact AngleMeasurements

50 mg of each polymer were dissolved in 600 μL of MEK (83.3 mg/mL). Eachof the 4/2 FPOSS-MA Synthetic Blend MMA copolymers dissolved completelyto a clear solution. The polymer solutions were then coated onmicroscope slides by blade coating (˜50μ wet film thickness). Each FPOSScontaining copolymer coated to a milky film. The coatings were driedovernight. Contact angle measurements of water and hexadecane were takenusing a Kruss DSA100 drop shape analyzer (See FIGS. 3 and 4).

The following numbered clauses include embodiments that are contemplatedand non-limiting:

Although only a number of exemplary embodiments have been described indetail above, those skilled in the art will readily appreciate that manymodifications are possible in the exemplary embodiments withoutmaterially departing from the novel teachings and advantages.Accordingly, all such modifications are intended to be included withinthe scope of this disclosure as defined in the following Claims.

While the methods, equipment and systems have been described inconnection with specific embodiments, it is not intended that the scopebe limited to the particular embodiments set forth, as the embodimentsherein are intended in all respects to be illustrative rather thanrestrictive.

Unless otherwise expressly stated, it is in no way intended that anymethod set forth herein be construed as requiring that its steps beperformed in a specific order. Accordingly, where a method Claim doesnot actually recite an order to be followed by its steps or it is nototherwise specifically stated in the Claims or descriptions that thesteps are to be limited to a specific order, it is no way intended thatan order be inferred, in any respect.

As used in the specification and the appended Claims, the singular forms“a,” “an” and “the” include plural referents unless the context clearlydictates otherwise.

Ranges may be expressed herein as from “about” one particular value,and/or to “about” another particular value. When such a range isexpressed, another embodiment includes from the one particular valueand/or to the other particular value. Similarly, when values areexpressed as approximations, by use of the antecedent “about,” it willbe understood that the particular value forms another embodiment. Itwill be further understood that the endpoints of each of the ranges aresignificant both in relation to the other endpoint, and independently ofthe other endpoint.

“Optional” or “optionally” means that the subsequently described eventor circumstance may or may not occur, and that the description includesinstances where said event or circumstance occurs and instances where itdoes not.

Throughout the description and Claims of this specification, the word“comprise” and variations of the word, such as “comprising” and“comprises,” means “including but not limited to,” and is not intendedto exclude, for example, other additives, components, integers or steps.The word “exemplary” or “illustrative” means “an example of” and is notintended to convey an indication of a preferred or ideal embodiment.“Such as” is not used in a restrictive sense, but for explanatorypurposes.

Disclosed are components that can be used to perform the disclosedmethods, equipment and systems. These and other components are disclosedherein, and it is understood that when combinations, subsets,interactions, groups, etc., of these components are disclosed that whilespecific reference of each various individual and collectivecombinations and permutation of these may not be explicitly disclosed,each is specifically contemplated and described herein, for all methods,equipment and systems. This applies to all aspects of this applicationincluding, but not limited to, steps in disclosed methods. Thus, ifthere are a variety of additional steps that can be performed it isunderstood that each of these additional steps can be performed with anyspecific embodiment or combination of embodiments of the disclosedmethods.

It should further be noted that any patents, applications andpublications referred to herein are incorporated by reference in theirentirety.

The invention claimed is:
 1. A process for preparing a compound having aformula

wherein, R¹ is a long chain fluorinated alkyl; R² is selected from thegroup consisting of C₁-C₈ alkyl, C₂-C₈ alkenyl, C₂-C₈ alkynyl, C₆-C₁₀aryl, C₃-C₈ cycloalkyl, 5-7 membered heterocyclic and 5-7 memberedheteroaryl, wherein each hydrogen atom in R² is independently optionallysubstituted by an R³; each R³ is independently selected from the groupconsisting of halo, C₁-C₈ alkyl, C₂-C₈ alkenyl, C₂-C₈ alkynyl, C₆-C₁₀aryl, C₃-C₈ cycloalkyl, 5-7 membered heterocyclic, 5-7 memberedheteroaryl, —NCO, —OR⁴, —NR⁴R⁵, —OC(O)R⁴, —C(O)OR⁴, —C(O)R⁴, —OC(O)OR⁴,—C(O)NR⁴R⁵, —OC(O)NR⁴R⁵, —NR⁴C(O)R⁵, —NR⁴C(O)OR⁵ and —NR⁴C(O)NR⁴R⁵, andwhen R³ is C₁-C₈ alkyl, C₂-C₈ alkenyl, C₂-C₈ alkynyl, C₆-C₁₀ aryl, C₃-C₈cycloalkyl, 5-7 membered heterocyclic or 5-7 membered heteroaryl, eachhydrogen atom in R³ is independently optionally substituted by an R⁶;each R⁴ and R⁵ is independently selected from the group consisting ofhydrogen, C₁-C₈ alkyl, C₂-C₈ alkenyl, C₂-C₈ alkynyl, C₆-C₁₀ aryl, C₃-C₈cycloalkyl, 5-7 membered heterocyclic, and 5-7 membered heteroaryl,wherein each hydrogen atom in R⁴ and R⁵ is independently optionallysubstituted by an R⁶; each R⁶ is independently selected from the groupconsisting of halo, C₁-C₈ alkyl, C₂-C₈ alkenyl, C₂-C₈ alkynyl, C₆-C₁₀aryl, C₃-C₈ cycloalkyl, 5-7 membered heterocyclic, 5-7 memberedheteroaryl, —NCO, —OR⁷, —NR⁷R⁸, —OC(O)R⁷, —C(O)OR⁷, —C(O)R⁷, —OC(O)OR⁷,—C(O)NR⁷R⁸, —OC(O)NR⁷R⁸, —NR⁷C(O)R⁸, —NR⁷C(O)OR⁸ and NR⁷C(O)NR⁷R⁸, andwhen R⁶ is C₁-C₈ alkyl, C₂-C₈ alkenyl, C₂-C₈ alkynyl, C₆-C₁₀ aryl, C₃-C₈cycloalkyl, 5-7 membered heterocyclic or 5-7 membered heteroaryl, eachhydrogen atom in R⁶ is independently optionally substituted by an R⁹;each R⁷ and R⁸ is independently selected from the group consisting ofhydrogen, C₁-C₈ alkyl, C₂-C₈ alkenyl, C₂-C₈ alkynyl, C₆-C₁₀ aryl, C₃-C₈cycloalkyl, 5-7 membered heterocyclic and 5-7 membered heteroaryl,wherein each hydrogen atom in R⁷ and R⁸ is independently optionallysubstituted by one or more R⁹; each R⁹ is independently selected fromthe group consisting of hydrogen, halo, C₁-C₈ alkyl, C₂-C₈ alkenyl,C₂-C₈ alkynyl, C₆-C₁₀ aryl, C₃-C₈ cycloalkyl, 5-7 membered heterocyclic,5-7 membered heteroaryl, —NCO, —OR¹⁰, —NR¹⁰R¹¹, —OC(O)R¹⁰, —C(O)OR¹⁰,—C(O)R¹⁰, —OC(O)OR¹⁰, —C(O)NR¹⁰R¹¹, —OC(O)NR¹⁰R¹¹, —NR¹⁰C(O)R¹¹,—NR¹⁰C(O)OR¹¹ and —NR¹⁰C(O)NR¹⁰R¹¹, and when R⁹ is C₁-C₈ alkyl, C₂-C₈alkenyl, C₂-C₈ alkynyl, C₆-C₁₀ aryl, C₃-C₈ cycloalkyl, 5-7 memberedheterocyclic, C₃-C₈ cycloalkyl or 5-7 membered heteroaryl, each hydrogenin R⁹ is independently optionally substituted by a moiety selected fromthe group consisting of halo, —NCO, —OR¹⁰, —NR¹⁰R¹¹, —OC(O)R¹⁰,—C(O)OR¹⁰, —C(O)R¹⁰, —OC(O)OR¹⁰, —C(O)NR¹⁰R¹¹, —OC(O)NR¹⁰R¹¹,—NR¹⁰C(O)R¹¹, —NR¹⁰C(O)OR¹¹ and —NR¹⁰C(O)NR¹⁰R¹¹; each R¹⁰ and R¹¹ isindependently selected from the group consisting of H, C₁-C₈ alkyl,C₂-C₈ alkenyl and C₂-C₈ alkynyl, and when R¹⁰ or R¹¹ are C₁-C₈ alkyl,C₂-C₈ alkenyl or C₂-C₈ alkynyl, each hydrogen atom in R¹⁰ and R¹¹ isindependently optionally substituted by a fluorine atom; n is an integerfrom 1 to 7; and, each R¹ and R² is independently covalently attached ata silicon atom, comprising: (a) contacting a compound of the formulaR¹Si(OR^(A))₃ with a compound of the formula R²Si(OR^(A))₃, in thepresence of a base, wherein R^(A) is a C₁-C₈ alkoxy, and the R^(A) onR¹Si(OR^(A))₃ and R²Si(OR^(A))₃ can be the same or different.
 2. Theprocess of claim 1, wherein R² is C₁-C₈ alkyl, wherein each hydrogenatom in R² is independently optionally substituted by an R³.
 3. Theprocess of claim 1, wherein R³ is —NCO, —OR⁴, —OC(O)R⁴, —C(O)OR⁴,—C(O)R⁴ or —OC(O)OR⁴.
 4. The process of claim 1, wherein R⁴ is C₁-C₈alkyl and wherein each hydrogen atom in R⁴ is independently optionallysubstituted by an R⁶.
 5. The process of claim 1, wherein R⁴ is C₂-C₈alkenyl, wherein each hydrogen atom in R⁴ is independently optionallysubstituted by an R⁶.
 6. The process of claim 1, wherein R⁶ is C₁-C₈alkyl, —NCO, —OR⁷, —NR⁷R⁸, —OC(O)R⁷, —C(O)OR⁷, —C(O)R⁷ or —OC(O)OR⁷. 7.The process of claim 1, wherein R⁷ is C₁-C₈ alkyl, C₂-C₈ alkenyl, C₂-C₈alkynyl, C₆-C₁₀ aryl or 5-7 membered heteroaryl, wherein each hydrogenatom in R⁷ is independently optionally substituted by one or more R⁹. 8.The process of claim 1, wherein R⁹ is hydrogen or C₁-C₈ alkyl, and whenR⁹ is C₁-C₈ alkyl, R⁹ is optionally substituted by a —OC(O)R¹⁰.
 9. Theprocess of claim 1, wherein R¹⁰ is H or C₁-C₈ alkyl, and when R¹⁰ isC₁-C₈ alkyl, each hydrogen atom in R¹⁰ is independently optionallysubstituted by a fluorine atom.
 10. The process of claim 1, wherein R²is n-propyl, wherein each hydrogen atom in R² is independentlyoptionally substituted by an R³.
 11. The process of claim 10, wherein R³is —OC(O)R⁴ or —OC(O)OR⁴.
 12. The process of claim 11, wherein R⁴ ismethyl.
 13. The process of claim 11, wherein R⁴ is —CH═CH₂, wherein eachhydrogen atom in R⁴ is independently optionally substituted by an R⁶.14. The process of claim 13, wherein R⁶ is C₁-C₈ alkyl.
 15. The processof claim 14, wherein R⁶ is methyl.
 16. The process of claim 10, whereinthe long chain fluorinated alkyl is 8/2, 6/2 or 4/2.
 17. The process ofclaim 1, wherein the long chain fluorinated alkyl is 8/2, 6/2 or 4/2.18. The process of claim 1, wherein the base is potassium hydroxide ortetraethylammonium hydroxide.
 19. The process of claim 2, wherein R³ is—NH₂.
 20. The process of claim 19, wherein the base is potassiumhydroxide or tetraethylammonium hydroxide.